CN109093110B - Composite material and method for producing same - Google Patents

Composite material and method for producing same Download PDF

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Publication number
CN109093110B
CN109093110B CN201710468578.3A CN201710468578A CN109093110B CN 109093110 B CN109093110 B CN 109093110B CN 201710468578 A CN201710468578 A CN 201710468578A CN 109093110 B CN109093110 B CN 109093110B
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composite material
metal
nanocellulose
core
manufacturing
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CN109093110A (en
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蔡明志
何羽轩
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Winbond Electronics Corp
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Winbond Electronics Corp
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Priority to US15/871,027 priority patent/US20180362736A1/en
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Priority to US17/118,619 priority patent/US11920020B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0887—Tungsten

Abstract

The invention provides a composite material. The composite material includes a nanocellulose inner core and a metal outer shell. The surface of the nano-cellulose inner core is coated by the metal shell. The above composite material has a size of nanometer scale and high mechanical strength. In addition, the invention also provides a manufacturing method of the composite material. The size of the composite material can be controlled within the range of nanometer size, and the mechanical strength of the whole composite material can be improved. And the inner core of the nano-cellulose can be used as a supporting template, so that the phenomenon of metal fusion can be avoided to influence the electrical property.

Description

Composite material and method for producing same
Technical Field
The invention relates to a material and a manufacturing method thereof, in particular to a composite material and a manufacturing method thereof.
Background
With the technology being changed day by day, the printing technology is also upgraded, wherein the printed electronics technology and the related aspects thereof are wide, such as the fabrication of nano wires (nanowires), electrodes (electrodes), transparent conductive films (transparent conductive films), and the like.
However, the conductive ink for printing electrons usually consists of nano metal particles or nano metal flakes, and less one-dimensional nano metal material exists, because the diameter of the one-dimensional nano metal material is about tens of nanometers, and the length is about several micrometers. The oversized metal material may cause problems with nozzle clogging during printing. On the other hand, in the prior art, in order to form the conductive ink with small-sized metal material, the micro-channels are formed in the aluminum oxide layer, and then the metal material is filled by electrochemical deposition, and then the aluminum oxide layer template is removed, so the processing steps are complicated. In addition, the one-dimensional structure in the prior art is often broken into fragments or particles due to temperature rise, and the original shape is lost, so that the electrical property is changed and the conductive effect is reduced. Therefore, how to improve the nozzle clogging problem and simplify the process and maintain the electrical property is the subject of current research.
Disclosure of Invention
The present invention provides a composite material having a size of nanometer scale and high mechanical strength.
The present invention provides a method for manufacturing a composite material, by which a composite material having a nano-scale size and high mechanical strength can be manufactured.
The invention provides a composite material which comprises a nano-cellulose inner core and a metal outer shell. The surface of the nano-cellulose inner core is coated by the metal shell.
In some embodiments of the invention, the composite material has a length to diameter ratio of between 1.5:1 and 500: 1.
In some embodiments of the invention, the diameter of the composite material is between 2 nanometers and 200 nanometers.
In some embodiments of the invention, the length of the composite material is between 50 nanometers and 5000 nanometers.
In some embodiments of the invention, the material of the nanocellulose core comprises Cellulose Nanofilaments (CNF), Cellulose Nanocrystals (CNC), Bacterial Cellulose (BC), or a combination thereof.
In some embodiments of the invention, the nanocellulose inner core is solid.
In some embodiments of the invention, the nanocellulose inner core has a diameter between 2 nm and 200 nm.
In some embodiments of the invention, the material of the metal housing comprises gold, silver, palladium, platinum, ruthenium, copper, tungsten, nickel, aluminum, or combinations thereof.
In some embodiments of the invention, the metal housing has a thickness between 2 nm and 200 nm.
The invention provides a manufacturing method of a composite material, which comprises the following steps: providing a nanocellulose inner core; modifying the inner core of the nanocellulose; forming metal ions of metal seed crystal generation points on the surface of the modified nano-cellulose inner core; carrying out a first reduction reaction to reduce metal ions at the metal seed crystal generation points to form metal seed crystals; and carrying out a second reduction reaction, and reducing metal ions at the metal seed crystal generation points at the metal seed crystal to form the surface of the nano-cellulose inner core coated and modified by the metal shell.
In some embodiments of the invention, the step of modifying the nanocellulose core is to perform a substitution reaction with a metal on hydroxyl groups on the carbon of the nanocellulose core to form metal-substituted hydroxyl groups.
In some embodiments of the invention, the metal ion of the metal seed generation site is formed on a metal-substituted hydroxyl group.
In some embodiments of the invention, the step of modifying the nanocellulose core comprises a substitution reaction of the nanocellulose core with potassium hydroxide, sodium hydroxide.
In some embodiments of the present invention, the reducing agent for performing the first reduction reaction and the second reduction reaction comprises ascorbic acid (ascorbyl acid), hydrazine (hydrazine), sodium borate (sodium borohydrate), formaldehyde, glucose, sodium citrate, urea, diethanolamine, triethanolamine, methanol, ethanol, ethylene glycol, glycerol, or a combination thereof.
In some embodiments of the present invention, the metal ions forming the metal seed generation sites and the metal precursor performing the second reduction reaction include silver nitrate, silver nitrite, silver sulfate, silver chloride, silver perchlorate, silver cyanate, silver carbonate, silver acetate, gold sulfite, chloroauric acid, chloroplatinic acid, copper nitrate, copper sulfate, copper chloride, nickel sulfate, or a combination thereof.
In some embodiments of the invention, performing the second reduction reaction further comprises adding a polymer.
In some embodiments of the invention, the polymer comprises Polyvinylpyrrolidone (PVP), Polyvinyl alcohol (PVA), polyacrylic acid (PAA), or a combination thereof.
In some embodiments of the present invention, the reaction temperature for performing the first reduction reaction and the second reduction reaction is between 0 degrees celsius and 250 degrees celsius.
In some embodiments of the invention, the material of the metal housing comprises gold, silver, palladium, platinum, ruthenium, copper, tungsten, nickel, aluminum, or combinations thereof.
Based on the above, the composite material of the present invention includes a nanocellulose core and a metal shell, wherein the metal shell covers a surface of the nanocellulose core. From the structural point of view, the size of the composite material of the present invention can be controlled in the nanometer size range, so that the problem of blocking caused by over-size can be effectively reduced. In addition, in the composite material of the invention, because the nano-cellulose is used as the inner core and has high crystallinity, the mechanical strength of the whole composite material can be improved. And the inner core of the nano-cellulose can be used as a supporting template, so that the phenomenon of metal fusion can be avoided to influence the electrical property. From the processing point of view, in the manufacturing process of the composite material, the metal shell is defined by the nano-cellulose inner core, and the step of removing the nano-cellulose inner core is not needed subsequently, so the processing is simplified.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a schematic illustration of a composite material shown in accordance with some embodiments of the present invention;
FIGS. 2A-2E are schematic diagrams illustrating a process for manufacturing a composite material according to some embodiments of the present invention;
FIGS. 3A-3E are schematic views of the surface chemical structures of the composite materials of FIGS. 2A-2E, respectively;
fig. 4 is a flow diagram illustrating a method of manufacturing a composite material, in accordance with some embodiments of the present invention.
The reference numbers illustrate:
100: composite material
S10, S12, S14, S16, S18: step (ii) of
110. 110a, 110b, 110c, 110 d: nano cellulose inner core
112a, 112b, 112c, 112d, 112 e: surface of
120: metal shell
120 a: metal ion of metal seed crystal generation point
120 b: metal seed crystal
Detailed Description
FIG. 1 is a schematic illustration of a composite material shown in accordance with some embodiments of the present invention.
Referring to fig. 1, the composite material 100 of the present embodiment may include a nanocellulose core 110 and a metal shell 120. The metal outer shell 120 covers the surface of the nanocellulose inner core 110.
< inner core of nanocellulose >
The material of the nanocellulose core 110 includes, for example, Cellulose Nanofibrils (CNF) derived from plants, algae or bacteria, Cellulose Nanocrystals (CNC), Bacterial Cellulose (BC), or a combination thereof. In some embodiments, the material of the nanocellulose inner core 110 is, for example, crystalline cellulose. In some embodiments, the molecular weight of the nanocellulose inner core 110 is, for example, between 500 to 500000. In some embodiments, the diameter of the nanocellulose inner core 110 is, for example, between 2 nanometers to 200 nanometers. In other embodiments, the nanocellulose inner core 110 has a diameter of, for example, less than 5 nanometers. In some embodiments, the length of the nanocellulose inner core 110 is, for example, between 20 nm and 20000 nm. In some embodiments, the ratio of the length to the diameter of the nanocellulose inner core 110 is, for example, between 10:1 to 1000: 1. In other embodiments, the ratio of the length to the diameter of the nanocellulose inner core 110 is, for example, 60:1, although the invention is not limited thereto. The chemical formula of cellulose is as follows:
Figure BDA0001326518660000051
< Metal case >
The material of the metal housing 120 includes, for example, a noble metal. In some embodiments, the material of the metal housing 120 includes, for example, gold, silver, palladium, platinum, ruthenium, copper, tungsten, nickel, aluminum, or a combination thereof. In some embodiments, the thickness of the metal housing 120 is, for example, between 2 nanometers and 200 nanometers.
< composite Material >
In some embodiments, the diameter of the composite 100 formed by the nanocellulose inner core 110 and the metal outer shell 120 is, for example, between 2 nm and 200 nm. In some embodiments, the length of the composite material 100 is, for example, between 50 nanometers and 5000 nanometers. In some embodiments, the length to diameter ratio of composite material 100 is, for example, between 1.5:1 and 500: 1. In other embodiments, the length to width ratio of composite material 100 is, for example, 60:1, although the invention is not limited thereto.
In some embodiments, the nanocellulose inner core 110 may be solid. That is, since the nanocellulose core 110 is solid, the overall composite material 100 can have a rigid structure. It is worth mentioning that the surface of the composite material 100 is covered by the metal shell 120, so that the entire composite material 100 has the conductive property.
Fig. 2A-2E are schematic diagrams illustrating a manufacturing process of a composite material according to some embodiments of the invention. Fig. 3A to 3E are schematic surface chemical structures of the composite materials of fig. 2A to 2E, respectively. Fig. 4 is a flow diagram illustrating a method of manufacturing a composite material, in accordance with some embodiments of the present invention.
Referring to fig. 2A to 2E, fig. 3A to 3E, and fig. 4, a method for manufacturing the composite material 100 of the present invention includes: providing a nanocellulose inner core 110a (step S10); modifying the nanocellulose inner core 110a (step S12); forming metal ions 120a of metal seed generation points on the surface 112b of the modified nanocellulose core 110b (step S14); performing a first reduction reaction to reduce the metal ions 120a of the metal seed crystal generation sites to form metal seed crystals 120b (step S16); and performing a second reduction reaction to reduce the metal ions 120b at the metal seed crystal generating sites to form a metal shell 120 covering the surface of the modified nanocellulose core (step S18). The above steps will be described in more detail below.
< step S10>
Referring to fig. 2A, fig. 3A and fig. 4, first, step S10 is performed to provide a nanocellulose core 110 a. In some embodiments, the method of forming the nanocellulose inner core 110a includes, for example, physical methods, chemical methods, or a combination thereof. For example, in some embodiments, the nanocellulose core 110a is formed, for example, by physical treatment followed by chemical treatment to obtain a highly crystalline nanocellulose core 110 a. In some embodiments, physical methods include, for example, treatment using a grinder (grinder), homogenizer (homogenerizer), microfluidizer (microfluidizer), or the like; the chemical method is, for example, a single-step or multi-step hydrolysis reaction such as sulfuric acid hydrolysis or hydrochloric acid hydrolysis, or the like. The diameter, length, material, etc. of the nanocellulose core 110a are as same as those of the nanocellulose core 110, and are not described herein again. After hydrolysis, the carbon of the inner nanocellulose core 110a has hydroxyl groups. In one embodiment, the hydroxyl (-OH) group of the carbon (C6) at the 6-position of the nanocellulose core 110a is, for example, a primary hydroxyl (-CH) group after hydrolysis2OH). That is, the surface 112a of the nanocellulose core 110a has a plurality of hydroxyl groups (represented by C6-OH) of carbon (C6) at the 6-position of the nanocellulose core for subsequent reaction, but the present invention is not limited thereto. Herein, for convenience of explanation, the hydroxyl group of the carbon at the 6-position of the nanocellulose core 110a is exemplified, but the present invention is not limited thereto.
< step S12>
Referring to fig. 2B, fig. 3B and fig. 4, step S12 is performed to modify the nanocellulose core 110 a. In some embodiments, the method of modifying the inner nanocellulose core 110a is, for example, using a metal hydroxide (M (OH)nWhere M is a metal, e.g., K, and n is the valence number of the metal) solution treats the surface 112a of the nanocellulose core 110a to replace the hydrogen of the hydroxyl group (C6-OH) of the carbon at the 6-position thereof with the metal (M) of the metal hydroxide, thereby forming OM groups. That is, the surface 112b of the modified nanocellulose core 110b has OM groups attached to the modified nanocellulose core110b at carbon (C6) in position 6 (represented by C6-OM). The OM group is, for example, OK.
In some embodiments, the metal hydroxide (M (OH)nIncluding, for example, potassium hydroxide (KOH). In one embodiment, the modified nanocellulose core 110a is, for example, prepared by treating the surface 112a of the nanocellulose core 110a with potassium hydroxide to replace the hydroxyl group (C6-OH) of the carbon at the 6-position with an OK group, but the invention is not limited thereto. In some embodiments, the modified nanocellulose inner core 110a does not have substitution reaction on all hydroxyl groups of the nanocellulose inner core 110a, that is, only a portion of the hydroxyl groups of the nanocellulose inner core 110a have substitution reaction to form OM group, but the invention is not limited thereto.
< step S14>
Referring to fig. 2C, fig. 3C and fig. 4, step S14 is performed to form metal ions 120a of metal seed crystal generation points on the surface 112b of the modified nanocellulose core 110 b. In some embodiments, when the surface 112b of the modified nanocellulose core 110b has OM groups, the solution containing the metal precursor (M ') may be used to treat the surface 112b of the modified nanocellulose core 110b such that the OM groups on the surface 112b are replaced with OM' groups. That is, in this case, the surface 112C of the nanocellulose core 110C has OM 'group, and the OM' group is connected to the carbon (C6) (represented by C6-OM ') at the 6-position of the nanocellulose core 110C, and the OM' group can be used as a metal ion source for the generation site of the subsequent metal seed crystal growth. The OM' group is, for example, OAg.
In some exemplary embodiments, M is, for example, potassium (K) and M' is, for example, silver (Ag). In some embodiments, the solution containing the metal precursor M' includes, for example, silver nitrate (AgNO)3) Silver nitrite (AgNO)2) Silver sulfate (Ag)2SO4) Silver chloride (AgCl), silver perchlorate (AgClO)4) Silver cyanate (AgOCN), silver carbonate (Ag)2CO3) Silver acetate (AgC)2H3O2) Gold sulfite (Au (SO)3)2 2-) Chloroauric acid (HAuCl)4) Chloroplatinic acid (H)2PtCl6) Copper nitrate (Cu (NO)3)2) Copper sulfate (CuSO)4) Copper chloride (CuCl)2) Nickel sulfate (NiSO)4) Or a combination thereof. In one embodiment, the surface 112b of the modified nanocellulose core 110b has OK groups, and then, the OK groups on the surface of the modified nanocellulose core 110b may be replaced with OAg groups by treating the surface 112b with, for example, silver nitrate.
< step S16>
Referring to fig. 2D, fig. 3D and fig. 4, step S16 is performed to perform a first reduction reaction to reduce the metal ions 120a at the metal seed crystal generation sites to form metal (atom) seed crystals 120 b. That is, the surface 112d of the nanocellulose inner core 110d has a plurality of metal seeds 120 b. In some exemplary embodiments, the plurality of metal seeds 120b are, for example, silver atom seeds.
In some embodiments, the reducing agent that reduces the metal ion 120a of the metal seed crystal generation site is, for example, ascorbic acid (ascorbyl acid), hydrazine (hydrazine), sodium borate (sodium borohydrate), formaldehyde, glucose, sodium citrate, urea, diethanolamine, triethanolamine, methanol, ethanol, ethylene glycol, glycerol, or a combination thereof. In some embodiments, the reaction temperature for reducing the metal ion 120a at the metal seed generation point is, for example, between 0 degrees celsius and 250 degrees celsius, such as performing the reduction reaction in an ice bath, a heated environment, or at room temperature.
In one specific exemplary embodiment, the surface 112a of the nanocellulose core 110a is treated with potassium hydroxide to replace its hydroxyl groups (C6-OH) with OK groups (step S12). Next, the surface 112b of the modified nanocellulose core 110b is treated with a silver nitrate solution to replace the OK groups on the surface 112b with OAg groups (step S14). Thereafter, the OAg group is reduced to Ag atoms using ascorbic acid as a reducing agent to serve as an Ag metal seed crystal (step S16).
< step S18>
Referring to fig. 2E, fig. 3E and fig. 4, step S18 is performed to perform a second reduction reaction, so as to reduce the metal seed crystal 120b to form a metal shell 120 covering the modified surface of the nanocellulose core, that is, the metal shell 120 is covered on the surface 112E of the nanocellulose core 110 d. In detail, the second reduction reaction is performed by performing the second metal growth using the metal seed crystal 120b as a growth point and the metal precursor and the reducing agent, and the types of the metal precursor and the reducing agent and the temperature of the reduction reaction are as described above, and thus are not described again. In some embodiments, the second reduction reaction may additionally add a polymer, such as Polyvinylpyrrolidone (PVP), Polyvinyl alcohol (PVA), polyacrylic acid (PAA), or a combination thereof. The thickness, material, etc. of the metal housing 120 are as described above, and will not be described herein.
The composite material of the present invention can be used as a material in conductive ink, for example. It is worth mentioning that the composite material of the present invention can be formed into a desired size range by controlling the size (diameter, length, etc.) of the nanocellulose core. For example, the length of the composite material can be controlled between 50 nm and 5000 nm, so that the problem of nozzle blockage of the conductive ink in the printing process can be effectively solved. In addition, in the composite material of the invention, the nano-cellulose is used as the inner core, and the nano-cellulose has high crystallinity, so the mechanical strength of the whole composite material can be improved. And the inner core of the nano-cellulose can be used as a supporting template, so that the phenomenon of metal fusion can be avoided to influence the electrical property.
In addition, in the manufacturing process of the composite material of the present invention, after the nanocellulose core is formed, the surface of the nanocellulose core is then coated with the metal shell, and then the step of removing the nanocellulose core is not required. That is, if the composite material of the present invention is used as a material of conductive ink, a conductive circuit can be directly formed by spray printing, and the nano cellulose inner core does not need to be removed subsequently, so that the processing can be simplified.
In summary, the composite material of the present invention includes a nanocellulose inner core and a metal shell, wherein the metal shell covers a surface of the nanocellulose inner core. From the structural point of view, the size of the composite material of the present invention can be controlled in the nanometer size range, so that the problem of blocking caused by over-size can be effectively reduced. In addition, in the composite material of the invention, because the nano-cellulose is used as the inner core and has high crystallinity, the mechanical strength of the whole composite material can be improved. And the inner core of the nano-cellulose can be used as a supporting template, so that the phenomenon of metal fusion can be avoided to influence the electrical property. From the processing point of view, in the manufacturing process of the composite material, the metal shell is defined by the nano-cellulose inner core, and the step of removing the nano-cellulose inner core is not needed subsequently, so the processing is simplified.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.

Claims (18)

1. A method of manufacturing a composite material, comprising:
providing a nanocellulose inner core;
modifying the nanocellulose inner core;
forming metal ions of metal seed crystal generation points on the surface of the modified nano-cellulose inner core;
carrying out a first reduction reaction to reduce the metal ions at the metal seed crystal generation points to form metal seed crystals; and
performing a second reduction reaction, reducing metal ions at the metal seed crystal generation point to form a metal shell to cover the surface of the modified nanocellulose inner core,
wherein the step of modifying the nanocellulose core is to perform a substitution reaction with a metal on hydroxyl groups on the carbon of the nanocellulose core to form metal-substituted hydroxyl groups.
2. The method for producing a composite material according to claim 1, wherein the metal ion of the metal seed crystal generation site is formed on the metal-substituted hydroxyl group.
3. The method of manufacturing a composite material according to claim 1, wherein the step of modifying the nanocellulose core comprises a substitution reaction of the nanocellulose core with potassium hydroxide.
4. The method of manufacturing a composite material according to claim 1, wherein the reducing agent for performing the first reduction reaction and the second reduction reaction includes ascorbic acid, hydrazine, sodium borohydride, formaldehyde, glucose, sodium citrate, urea, diethanolamine, triethanolamine, methanol, ethanol, ethylene glycol, glycerol, or a combination thereof.
5. The method for producing a composite material according to claim 1, wherein the metal ions forming the metal seed crystal generation sites and the metal precursor performing the second reduction reaction include silver nitrate, silver nitrite, silver sulfate, silver chloride, silver perchlorate, silver cyanate, silver carbonate, silver acetate, gold sulfite, chloroauric acid, chloroplatinic acid, copper nitrate, copper sulfate, copper chloride, nickel sulfate, or a combination thereof.
6. The method of manufacturing a composite material according to claim 1, wherein performing the second reduction reaction further comprises adding a polymer.
7. The method of manufacturing a composite material according to claim 6, wherein the polymer comprises polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, or a combination thereof.
8. The method according to claim 1, wherein the reaction temperature for performing the first reduction reaction and the second reduction reaction is between 0 ℃ and 250 ℃.
9. The method of claim 1, wherein the material of the metal shell comprises gold, silver, palladium, platinum, ruthenium, copper, tungsten, nickel, aluminum, or a combination thereof.
10. The method of manufacturing a composite material according to claim 1, wherein the composite material comprises:
the nano-cellulose inner core, wherein the chemical formula of the cellulose is as follows; and
Figure FDA0003114230740000021
the metal shell coats the surface of the nano-cellulose inner core.
11. The method of manufacturing a composite material according to claim 1, wherein the ratio of the length to the diameter of the composite material is between 1.5:1 and 500: 1.
12. The method of manufacturing a composite material according to claim 1, wherein the diameter of the composite material is between 2 nm and 200 nm.
13. The method of manufacturing a composite material according to claim 1, wherein the length of the composite material is between 50 nm and 5000 nm.
14. The method of claim 1, wherein the material of the nanocellulose inner core comprises cellulose nano cilia, cellulose nano crystals, bacterial cellulose, or a combination thereof.
15. The method of manufacturing a composite material according to claim 1, wherein the nanocellulose core is solid.
16. The method of manufacturing a composite material according to claim 1, wherein the diameter of the nanocellulose core is between 2 and 200 nm.
17. The method of claim 10, wherein the material of the metal shell comprises gold, silver, palladium, platinum, ruthenium, copper, tungsten, nickel, aluminum, or a combination thereof.
18. The method of claim 1, wherein the metal shell has a thickness of between 2 nm and 200 nm.
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